Fungicides

ABSTRACT

Compounds having formula (I) ##STR1## wherein R 1 , R 2  and A are defined as in the specification. The compounds are useful as fungicides.

This application is a 371 of PCT/GB92/00681, filed Apr. 14, 1992.

This invention relates to derivatives of propenoic acid useful asfungicides, to processes for preparing them, to compositions containingthem, and to methods of using them to combat fungi, especially fungalinfections of plants.

There are described in EP-A-0 370 629 fungicidal derivatives ofpropenoic acid which have the general formula (I) wherein A is hydrogen,halo, hydroxy, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy,C₁₋₄ alkylcarbonyl, C₁₋₄ alkoxycarbonyl, phenoxy, nitro or cyano; R¹ andR², which may be the same or different, are hydrogen, optionallysubstituted alkyl, optionally substituted cycloalkyl, optionallysubstituted heterocyclylalkyl, optionally substituted cycloalkylalkyl,optionally substituted aralkyl, optionally substituted heteroarylalkyl,optionally substituted aryloxyalkyl, optionally substitutedheteroaryloxyalkyl, optionally substituted alkenyl, optionallysubstituted alkynyl, optionally substituted alkoxy, optionallysubstituted aryl, optionally substituted heteroaryl, optionallysubstituted aryloxy, optionally substituted heteroaryloxy, nitro, halo,cyano, --NR³ R⁴, --CO₂ R³, --CONR³ R⁴, --COR³, --S(O)_(n) R³ wherein nis 0, 1 or 2, (CH₂)_(m) PO(OR³)₂ wherein m is 0 or 1, or and R¹ and R²join to form a carbocyclic or heterocyclic ring system; and R³ and R⁴,which may be the same or different, are hydrogen, optionally substitutedalkyl, optionally substituted aralkyl, optionally substituted alkenyl,optionally substituted alkynyl, optionally substituted aryl oroptionally substituted heteroaryl. The compounds contain at least onecarbon-carbon double bond and one carbon-nitrogen double bond and existin the form of geometric isomers. The isomers which result from theunsymmetrically substituted double bonds of the propenoate group and theoxime ether are identified by the commonly used terms, "E" and "Z".

The present invention provides a compound of formula (I) wherein R¹ is:

(i) pyrid-2-yl substituted by one or more groups selected from C₁₋₆alkoxy, C₁₋₆ haloalkyl, C₁₋₆ haloalkoxy, C₁₋₄ alkoxy(C₁₋₆)alkyl or C₁₋₄alkoxy(C₁₋₆)alkoxy;

(ii) the group (A) wherein Y¹ is C₂₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆alkoxy, C₁₋₆ alkylthio, C₁₋₆ alkylsulphinyl, C₁₋₆ haloalkoxy, C₁₋₆alkoxy(C₁₋₆)alkyl, C₁₋₆ alkoxy(C₁₋₆)alkoxy, C₁₋₄alkoxy(C₁₋₆)alkoxy(C₁₋₆)alkoxy, di(C₁₋₄ alkoxy)(C₁₋₆)alkoxy, C₂₋₆alkenyloxy or C₂₋₆ alkynyloxy and Z¹ is hydrogen, fluorine, chlorine orC₁₋₆ alkyl; or Y¹ is methyl and Z¹ is fluorine, chlorine or C₁₋₆ alkyl;or,

(iii) the group (B) wherein Y² is C₂₋₆ alkyl, C₁₋₆ haloalkyl, C₂₋₆alkoxy, C₁₋₆ alkylthio, C₁₋₆ alkylsulphinyl, C₁₋₆ haloalkoxy or C₂₋₄alkynyloxy and Z² is hydrogen, fluorine, chlorine or C₁₋₄ alkyl; or Y²is methyl or methoxy and Z² is fluorine, chlorine or C₁₋₄ alkyl.

The compounds of the invention contain at least one carbon-carbon doublebond, and are sometimes obtained in the form of mixtures of geometricisomers. However these mixtures can be separated into individualisomers, and this invention embraces such isomers, and mixtures thereofin all proportions.

The individual isomers which result from the unsymmetrically substituteddouble bond of the propenoate group are identified by the commonly usedterms "E" and "Z". These terms are defined according to theCahn-Ingold-Prelog system which is fully described in the literature(see, for example, J March, "Advanced Organic Chemistry", 3rd edition,Wiley-Interscience, page 109 et seq).

For the carbon-carbon double bond of the propenoate group, usually oneisomer is more active fungicidally than the other, the more activeisomer usually being the one wherein the group --CO₂ CH₃ and --OCH₃ areon opposite sides of the olefinic bond of the propenoate group (the(E)-isomer). These (E)-isomers form a preferred embodiment of thisinvention.

Halogen includes fluorine, chlorine, bromine, and iodine.

Alkyl and the alkyl moieties of alkoxy, haloalkyl and haloalkoxy can bein the form of straight or branched chains and, unless otherwise stated,suitably contain from 1 to 6 carbon atoms. Examples are methyl, ethyl,iso-propyl and tert-butyl.

Examples of haloalkyl and the haloalkyl moiety of haloalkoxy aredifluoromethyl, trifluoromethyl, 2,2-difluoroethyl,2,2,2-trifluoroethyl, 1,1,2,2-tetrafluoroethyl, pentafluoroethyl,2,2,3,3-tetrafluoroprop-1-yl, 2,2,3,3,3-pentafluoroprop-1-yl,1,1,1-trifluoroprop-2-yl and 4-fluorobut-1-yl.

Alkenyl and alkynyl moieties of alkenyloxy and alkynyloxy suitablycontain from 2 to 6 carbon atoms, typically 2 to 4 carbon atoms, in theform of straight or branched chains. Examples are ethenyl, allyl andpropargyl.

In one aspect the present invention provides a compound of formula (I)wherein Y¹ is C₂₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ alkylthio,C₁₋₆ alkylsulphinyl, C₁₋₆ haloalkoxy or C₂₋₄ alkynyloxy and Z¹ ishydrogen, fluorine, chlorine or C₁₋₄ alkyl; or Y¹ is methyl and Z¹ isfluorine, chlorine or C₁₋₄ alkyl.

In another aspect the present invention provides a compound of formula(I) wherein Y¹ is C₂₋₆ alkoxy or C₁₋₆ haloalkoxy and Z¹ is hydrogen,chlorine, fluorine or methyl.

In a further aspect the present invention provides a compound of formula(I) wherein Y² is C₂₋₆ alkoxy or C₁₋₆ haloalkoxy and Z² is hydrogen,chlorine, fluorine or methyl.

According to the present invention there are provided the individualCompounds Nos 1 to 118 having the general formula (I) and the values ofR¹ given in Table I. All of the compounds in Table I are(E)-propenoates.

                                      TABLE I                                     __________________________________________________________________________    Compound                             Melting                                  No.   R.sup.1                   Olefinic.sup.+                                                                     Point °C.                         __________________________________________________________________________     1    6-OC.sub.2 H.sub.5 -pyrimidin-4-yl                                                                      7.60 87-88                                     2    6-CF.sub.3 -pyrid-2-yl    7.60 Oil                                       3    6-CF.sub.3 -pyrimidin-4-yl                                                                              7.62 87.2-88.4                                 4    4-CF.sub.3 -pyrid-2-yl    7.61 Oil                                       5    4-CF.sub.3 -pyrimidin-2-yl                                                                              7.58 Oil                                       6    4-C.sub.2 H.sub.5 O-pyrimidin-2-yl                                                                      7.58 87-89                                     7    6-C.sub.2 F.sub.5 -pyrimidin-4-yl                                                                       7.61 Oil                                       8    4-CH.sub.3 O-pyrid-2-yl   7.60 60-62                                     9    4-CH.sub.3 S-pyrimidin-2-yl                                                                             7.57 79-81                                    10    4-CH.sub.3 O-pyrimidin-2-yl                                                                             7.58 Oil                                      11    4-propargyloxy-pyrimidin-2-yl                                                                           7.58 Solid                                    12    4- -n-C.sub.3 H.sub.7 O-pyrimidin-2-yl                                                                  7.58 Oil                                      13    4- -n-butyloxy-pyrimidin-2-yl                                                                           7.58 Oil                                      14    3-CF.sub.3 -pyrid-2-yl    7.59 gum                                      15    4-iso-propyloxypyrimidin-2-yl                                                                           7.58 75-77                                    16    4-C.sub.2 H.sub.O-pyrid-2-yl                                                                            7.59 gum                                      17    4-C.sub.2 H.sub.5 S-pyrimidin-2-yl                                                                      7.58 77-79                                    18    3-CH.sub.3 O-pyrid-2-yl   7.58 97.1-98.7                                19    3-C.sub.2 H.sub.5 O-pyrid-2-yl                                                                          7.57 83.6-84.3                                20    6-CH.sub.3 O-pyrid-2-yl   7.60 106.2- 107.4                             21    6-C.sub.6 H.sub.5 -pyrimidin-4-yl                                                                       7.61 105.4-108                                22    4-C.sub.2 H.sub.5 O-5-CH.sub.3 -pyrimidin-2-yl                                                          7.58 80-82                                    23    4-iso-propyloxy-pyrid-2-yl                                                                              7.60 Oil                                      24    6-iso-propyloxy-pyrimidin-4-yl                                                                          7.59 Oil                                      25    4-CF.sub.3 CH.sub.2 O-pyrimidin-2-yl                                                                    7.59 90-92                                    26    4-sec-butyloxy-pyrimidin-2-yl                                                                           7.59 Gum                                      27    4-CH.sub.3 OC.sub.2 H.sub.4 O-pyrid-2-yl                                                                7.60 Gum                                      28    4-CH.sub.3 O-5-CH.sub.3 -pyrimidin-2-yl                                                                 7.79 105-106                                  29    5-CF.sub.3 -pyrid-2-yl    7.60 Gum                                      30    4-iso-propyloxy-5-CH.sub.3 -pyrimidin-2-yl                                                              7.58 Gum                                      31    4-CF.sub.3 CH.sub.2 O-5-CH.sub.3 -pyrimidin-2-yl                                                        7.59 130-131                                  32    6-C.sub.2 H.sub.5 O-pyrid-2-yl                                                                          7.60 64.4-65.6                                33    4-CH.sub.2 H.sub.5 O-5-F-pyrimidin-2-yl                                                                 7.58 100-102                                  34    4-CH.sub.3 O-5-F-pyrimidin-2-yl                                                                         7.58 79-81                                    35    6-CF.sub.3 CH.sub.2 O-pyrimidin-4-yl                                                                    7.61 Gum                                      36    4-CF.sub.3 -6-CF.sub.3 CH.sub.2 O-pyrid-2-yl                                                            7.61 84.1-85.1                                37    4-CF.sub.3 CH.sub.2 O-5-F-pyrimidin-2-yl                                                                7.58 88-89                                    38    4-iso-propyloxy-5-F-pyrimidin-2-yl                                                                      7.58 89-91                                    39    4-CF.sub.3 -6-C.sub.2 H.sub.5 O-pyrid-2-yl                                                              7.60 Gum                                      40    4-CHF.sub.2 CF.sub.2 CH.sub.2 O-pyrimidin-2-yl                                                          7.58 76-78                                    41    4-CF.sub.3 -6-CH.sub.3 O-pyrid-2-yl                                                                     7.61 80.3-80.8                                42    4-CF.sub.3 CH.sub.2 O-pyrid-2-yl                                                                        7.60 130.0-131.8                              43    5-iso-propyl-6-CH.sub.3 O-pyrimidin-4-yl                                                                7.58 Gum                                      44    4-iso-butyloxy-pyrimidin-2-yl                                                                           7.58 65-68                                    45    5-C.sub.2 H.sub.5 -6-CF.sub.3 -pyrimidin-4-yl                                                           7.59 Gum                                      46    4-tert-butyloxy-pyrimidin-2-yl                                                                          7.58 Gum                                      47    4-C.sub.2 H.sub.5 O-5-Cl-pyrimidin-2-yl                                                                 7.58 120-122                                  48    4-allyloxy-pyrimidin-2-yl 7.57 Gum                                      49    4-iso-propyloxy-5-Cl-pyrimidin-2-yl                                                                     7.58 90-92                                    50    4-CF.sub.3 CH.sub.2 O-5-Cl-pyrimidin-2-yl                                                               7.58 114-115                                  51    4-CF.sub.3 CF.sub.2 CH.sub.2 O-pyrimidin-2-yl                                                           7.59 108-110                                  52    4-(2-methylprop-2-enyl)oxy-pyrimidin-2-yl                                                               7.58 Gum                                      53    6-CF.sub.3 CH(CH.sub.3)O-pyrimidin-4-yl                                                                 7.62 Gum                                      54    4-CH.sub.3 O-5-Cl-pyrimidin-2-yl                                                                        7.58 134-6                                    55    4-CHF.sub.2 CH.sub.2 O-pyrimidin-2-yl                                   56    4-CH.sub.2 FCH.sub.2 CH.sub.2 O-pyrimidin-2-yl                          57    4-CF.sub.3 CH(CH.sub.3)O-pyrimidin-2-yl                                 58    4-CH.sub.2 FCH.sub.2 CH.sub.2 CH.sub.2 O-pyrimidin-2-yl                 59    4-CF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 O-pyrimidin-2-yl                  60    4-CF.sub.3 CF.sub.2 CH(CH.sub.3)O-pyrimidin-2-yl                        61    4-CHF.sub.2 CF.sub.2 CH(CH.sub.3)O-pyrimidin-2-yl                       62    4-CH.sub.3 CHFCF.sub.2 CH.sub.2 O-pyrimidin-2-yl                        63    4-CF.sub.3 CF.sub.2 CF.sub.2 CH.sub.2 O-pyrimidin-2-yl                  64    4-CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 O-pyrimidin-2-yl                  65    4-CH.sub.3 OCH.sub.2 CH.sub.2 O-pyrimidin-2-yl                          66    4-CH.sub.3 CH.sub.2 OCH.sub.2 CH.sub.2 O-pyrimidin-2-yl                                                 7.57 Gum                                      67    4-CH.sub.3 (CH.sub.2).sub.4 O-pyrimidin-2-yl                            68    4-CH.sub.3 (CH.sub.2).sub.2 CH(CH.sub.3)O-pyrimidin-2-yl                69    4-iso-propyl-6-C.sub.2 H.sub.5 O-pyrimidin-4-yl                         70    5-iso-propyl-6-CF.sub.3 CH.sub.2 O-pyrimidin-4-yl                       71    6-(CF.sub.3).sub.2 CHO-pyrimidin-4-yl                                   72    6-CHF.sub.2 CH.sub.2 O-pyrimidin-4-yl                                   73    6-CH.sub.2 FCH.sub.2 CH.sub.2 O-pyrimidin-4-yl                          74    6-CH.sub.2 FCH.sub.2 CH.sub.2 CH.sub.2 O-pyrimidin-4-yl                   75.sup.˜                                                                    6-CF.sub.3 CH.sub.2 CH.sub.2 CH.sub.2 O-pyrimidin-4-yl                  76    6-CF.sub.3 CF.sub.2 CH(CH.sub.3)O-pyrimidin-4-yl                        77    6-CHF.sub.2 CF.sub.2 CH(CH.sub.3)O-pyrimidin-4-yl                       78    6-CF.sub.3 CHFCF.sub.2 CH.sub.2 O-pyrimidin-4-yl                        77    6-CF.sub.3 CF.sub.2 CF.sub.2 CH.sub.2 O-pyrimidin-4-yl                  78    6-CF.sub.3 CHFCF.sub.2 CH.sub.2 O-pyrimidin-4-yl                        79    6-CF.sub.3 CF.sub.2 CF.sub.2 CH.sub.2 O-pyrimidin-4-yl                  80    5-F-6-CF.sub.3 CH.sub.2 O-pyrimidin-4-yl                                81    5-Cl-6-CF.sub.3 CH.sub.2 O-pyrimidin-4-yl                               82    5-CH.sub.3 -6-CF.sub.3 CH.sub.2 O-pyrimidin-4-yl                        83    5-CH.sub.3 CH.sub.2 -6-CF.sub.3 CH.sub.2 O-pyrimidin-4-yl               84    5-CH.sub.3 CH.sub.2 CH.sub.2 -6-CF.sub.3 CH.sub.2 -pyrimidin-4-yl       85    3-CH.sub.3 O-4-CF.sub.3 -pyrid-2-yl                                     86    3-CH.sub.3 CH.sub.2 O-4-CF.sub.3 -pyrid-2-yl                            87    5-CH.sub.3 CH.sub.2 O-pyrid-2-yl                                        88    4-CH.sub.3 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2 O-pyrimidin-2-yl        89    4-CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 O-pyrimidin-2-yl                 90    4-CH.sub.3 CH.sub.2 OCH.sub.2 CH.sub.2 CH(CH.sub.3 CH.sub.2)-O-pyrim          idin-2-yl                                                               91    4-CH.sub.3 OCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 CH.sub.2            O-pyrimidin-2-yl                                                        92    4-CH.sub.3 OCH(CH.sub.3)CH.sub.2 O-pyrimidin-2-yl                       93    4-CH.sub.3 CH.sub.2 OCH.sub.2 CH(CH.sub.2 OCH.sub.2 CH.sub.3)-O-pyri          midin-2-yl                                                              94    4-CH.sub.3 OCH.sub.2 CH(CH.sub.3)O-pyrimidin-2-yl                       95    4-CH.sub.3 (CH.sub.2).sub.3 OCH.sub.2 CH(CH.sub.3))-pyrimidin-2-yl      96    4-CH.sub.3 OCH.sub.2 CH(CH.sub.2 CH.sub.3)O-pyrimidin-2-yl              97    4-CH.sub.3 CH.sub.2 OCH.sub.2 CH(CH.sub.3)O-pyrimidin-2-yl              98    4-CH.sub.3 OCH.sub.2 O-pyrimidin-2-yl                                   99    4-CH.sub.3 CH.sub.2 OCH.sub.2 O-pyrimidin-2-yl                          100   4-CH.sub.3 CH.sub.2 OCH(CH.sub.3)O-pyrimidin-2-yl                       101   4-C.sub.2 H.sub.5 -pyrimidin-2-yl                                       102   4-allyloxy-5-CH.sub.3 -pyrimidin-2-yl                                   103   4,5-di-CH.sub.3 -pyrimidin-2-yl                                         104   4-(3-butenyloxy)-pyrimidin-2-yl                                         105   4-(2-methyl-2-propenyloxy)-pyrimidin-2-yl                               106   4-(2-butynyloxy)-pyrimidin-2-yl                                         107   4-(3-butynyloxy)-pyrimidin-2-yl                                          108.sup.˜                                                                    4-(3-buten-2-yloxy)-pyrimidin-2-yl                                       109.sup.˜                                                                    4-(2-butenyloxy)-pyrimidin-2-yl                                          110.sup.˜                                                                    4-(butyn-3-yloxy)-pyrimidin-2-yl                                        111   4-F.sub.2 CHO-pyrimidin-2-yl                                            112   6-F.sub.2 CHO-pyrimidin-4-yl                                            113   4-CF.sub.3 O-pyrimidin-2-yl                                             114   6-CF.sub.3 O-pyrimidin-4-yl                                             115   4-CHF.sub.2 CF.sub.2 O-pyrimidin-2-yl                                   116   6-CHF.sub.2 CF.sub.2 O-pyrimidin-4-yl                                   117   4-CCl.sub.3 O-pyrimidin-2-yl                                            118   6-CCl.sub.3 O-pyrimidin-4-yl                                            __________________________________________________________________________     .sup.+ Chemical shift of singlet from olefinic proton on methoxypropenoat     group of major oxime ether isomer (ppm from tetramethylsilane).               .sup.˜ In the form of a gum, NMR data given in Table II.           

The compounds of the invention are characterized by the melting pointsgiven in Table I and/or by the NMR data given in Table II.

                  TABLE II                                                        ______________________________________                                        SELECTED PROTON NMR DATA                                                      Com-                                                                          pound                                                                         No.   Proton NMR Data (δ)                                               ______________________________________                                         2    2.34(3H, s); 3.69(3H, s); 3.82(3H, s); 5.19(2H, s);                           7.10-7.60(5H, m); 7.60(1H, s); 7.79(1H, t); 8.08(1H, d)                       ppm.                                                                     5    2.40(3H, s); 3.68(3H, s); 3.82(3H, s); 5.35(2H, s);                           7.18(1H, m); 7.35(2H, m); 7.54(1H, m); 7.58(1H, s);                           7.60(1H, d); 9.07(1H, d) ppm.                                            7    2.30(3H, s); 3.68(3H, s); 3.83(3H, s); 5.25(2H, s);                           7.18(1H, m); 7.35(2H, m); 7.48(1H, m); 7.61(1H, s);                           8.22(1H, s); 9.33(1H, s) ppm.                                           10    2.35(3H, s); 3.68(3H, s); 3.82(3H, s); 4.03(3H, s);                           5.30(2H, s); 6.68(1H, d); 7.18(1H, m); 7.34(2H, m);                           7.54(1H, s); 7.58(1H, s); 8.50(1H, d) ppm.                              11    2.35(3H, s); 2.51(1H, m); 3.68(3H, s); 3.82(3H, s);                           5.05(2H, d); 5.32(2H, s); 6.76(1H, d); 7.18(1H, m);                           7.34(2H, m); 7.55(1H, m); 7.58(1H, s); 8.58(1H, d) ppm.                 12    1.03(3H, t); 1.81(2H, m); 2.35(3H, s); 3.68(3H, s);                           3.82(3H, s); 4.36(2H, t); 5.31(2H, s); 6.65(1H, d);                           7.18(1H, m); 7.35(2H, m); 7.55(1H, d); 7.58(1H, s);                           8.50(1H, d) ppm.                                                        13    0.99(3H, t); 1.48(2H, m); 1.78(2H, m); 2.35(3H, s);                           3.68(3H, s); 3.82(3H, s); 4.41(2H, t); 5.31(2H, s);                           6.65(1H, d); 7.18(1H, m); 7.32(2H, m); 7.55(1H, d);                           7.58(1H, s); 8.49(1H, d) ppm.                                           14    2.29(3H, s); 3.68(3H, s); 3.80(3H, s); 5.14(2H, s)                            7.16(1H, m); 7.28-7.43(3H, m); 7.51(1H, m); 7.59(1H, s);                      8.02(1H, d); 8.77(1H, d) ppm.                                           16    1.43(3H, t); 2.32(3H, s); 3.69(3H, s); 3.80(3H, s);                           4.10(2H, q); 5.19(2H, s); 6.75(1H, m); 7.16(1H, m);                           7.29-7.39(3H, m); 7.52(1H, m); 7.59(1H, s); 8.38(1H, d)                       ppm.                                                                    23    1.36(6H, d); 2.32(3H, s); 3.69(3H, s); 3.82(3H, s);                           4.69(1H, m); 5.18(2H, s); 6.73(1H, dd); 7.17(1H, m);                          7.28-7.37(3H, m); 7.52(1H, m); 7.60(1H, s); 8.38(1H, d)                       ppm.                                                                    24    1.35(6H, d); 2.26(3H, s); 3.69(3H, s); 3.82(3H, s);                           5.18(2H, s); 5.37(1H, m); 7.11(1H, s); 7.1-7.5(4H, m);                        7.59(1H, s); 8.73(1H, s) ppm.                                           26    0.98(3H, t); 1.36(3H, d); 1.72(2H, m); 2.32(3H, s);                           3.68(3H, s); 3.82(3H, s); 5.28(1H, m); 5.32(2H, s);                           6.61(1H, d); 7.18(1H, m); 7.35(2H, m); 7.55(1H, m);                           7.59(1H, s); 8.49(1H, d) ppm.                                           27    2.32(3H, s); 3.45(3H, s); 3.69(3H, s); 3.76(2H, t);                           3.82(3H, s); 4.20(2H, t); 5.18(2H, s); 6.81(1H, dd);                          7.17(1H, m); 7.29-7.37(2H, m); 7.42(1H, d); 7.51(1H, m);                      7.60(1H, s); 8.39(1H, d) ppm.                                           29    2.33(3H, s); 3.70(3H, s); 3.83(3H, s); 5.21(2H, s);                           7.18(1H, t); 7.34(2H, t); 7.50(1H, t); 7.60(1H, s);                           7.85(1H, dd); 8.02(1H, d); 8.82(1H, s) ppm.                             30    1.38(6H, d); 2.12(3H, s); 2.34(3H, s); 3.68(3H, S);                           3.82(3H, s); 5.29(2H, s); 5.47(1H, m); 7.18(1H, m);                           7.34(2H, m); 7.55(1H, m); 7.58(1H, s); 8.30(1H, s) ppm.                 35    2.27(3H, s); 3.70(3H, s); 3.85(3H, s); 4.81(2H, q);                           5.19(2H, s); 7.18(1H, m); 7.34(3H, m); 7.48(1H, m);                           7.61(1H, s); 8.86(1H, s) ppm.                                           39    1.40(3H, t); 2.28(3H, s); 3.69(3H, s); 3.84(3H, s);                           4.42(2H, q); 5.19(2H, s); 6.87(1H, s); 7.16(1H, m);                           7.34(2H, m); 7.51(1H, m); 7.60(1H, s); 7.67(1H, s) ppm.                 43    1.18(6H, d); 2.21(3H, s); 3.19(1H, sept); 3.67(3H, s);                        3.81(3H, s); 3.99(3H, s); 5.10(2H, s); 7.16(1H, m);                           7.33(2H, m); 7.48(1H, m); 7.57(1H, s); 8.59(1H, s) ppm.                 45    1.00(3H, t); 2.29(3H, s); 2.91(2H, q); 3.67(3H, s);                           3.82(3H, s); 5.16(2H, s); 7.17(1H, m); 7.34(2H, m);                           7.45(1H, m); 7.54(1H, s); 9.15(1H, s) ppm.                              46    1.61(9H, s); 2.30(3H, s); 3.68(3H, s); 3.82(3H, s);                           5.30(2H, s); 6.55(1H, d); 7.18(1H, m); 7.34(2H, m);                           7.55(1H, m); 7.58(1H, s); 8.45(1H, d) ppm.                              48    2.35(3H, s); 3.69(3H, s); 3.81(3H, s); 4.92(2H, d);                           5.2-5.5(1H, m); 5.31(2H, s); 6.0-6.2(1H, m);                                  6.70(1H, d); 7.1-7.6(4H, m); 7.57(1H, s); 8.53(1H, d) ppm.              52    1.83(3H, s); 2.35(3H, s); 3.69(3H, s); 3.82(3H, s);                           4.86(2H, s); 5.00(1H, s); 5.10(1H, s); 5.31(2H, s);                           6.72(1H, d); 7.1-7.6(4H, m); 7.58(1H, s); 8.54(1H, d) ppm.              53    1.50(3H, d); 2.27(3H, s); 3.71(3H, s); 3.85(3H, s);                           5.19(2H, s); 5.83(1H, sept); 7.09(1H, m); 7.28(1H, s);                        7.35(2H, m); 7.49(1H, m); 7.62(1H, s); 8.76(1H, s) ppm.                 66    1.24(3H, t); 2.34(3H, s); 3.60(2H, q); 3.68(3H, s);                           3.81(2H, m); 3.83(3H, s); 4.58(2H, m); 5.32(2H, s);                           6.74(1H, d); 7.1-7.6(4H, m); 7.57(1H, s); 8.53(1H, d) ppm.              75    2.06(2H, m); 2.27(3H, s); 2.27(2H, m); 3.70(3H, s);                           3.84(3H, s); 4.43(2H, t); 5.20(2H, s); 7.18(1H, m);                           7.20(1H, s); 7.35(2H, m); 7.49(1H, m); 7.61(1H, s);                           8.75(1H, s) ppm.                                                        108   1.45(3H, d); 2.32(3H, s); 3.68(3H, s); 3.82(3H, s);                           5.18(1H, d); 5.32(1H, d); 5.31(2H, s); 5.78(1H, m);                           5.92(1H, m); 6.62(1H, d); 7.17(1H, m); 7.33(2H, m);                           7.55(1H, m); 7.58(1H, s); 8.50(1H, d) ppm.                              109   1.77(3H, d); 2.34(3H, s); 3.68(3H, s); 3.82(3H, s);                           4.86(2H, d); 5.31(2H, s); 5.67-5.99(2H, m); 6.67(1H, d);                      7.15(1H, m); 7.34(2H, m); 7.54(1H, m); 7.58(1H, s);                           8.50(1H, d) ppm.                                                        110   1.66(3H, d); 2.36(3H, s); 2.47(1H, d); 3.68(3H, s);                           3.81(3H, s); 5.31(2H, s); 5.87(1H, m); 6.71(1H, d);                           7.1-7.6(4H, m); 7.57(1H, d); 8.56(1H, d) ppm.                           ______________________________________                                         Table II shows selected proton NMR data for certain compounds described i     Table I. Chemical shifts are measured in ppm from tetramethylsilane, and      deuterochloroform was used as solvent throughout. The operating frequency     of the NMR spectrometer was 270 MHz. The following abbreviations are used     s = singlet                                                                   sept = septet                                                                 d = doublet                                                                   m = multiplet                                                                 dd = double doublet                                                           br =  broad                                                                   t = triplet                                                                   ppm = parts per million                                                       q = quartet                                                              

The compounds of the invention of formula (I) may be prepared by thesteps shown in Scheme 1. The term R¹ is as defined above, and X is aleaving group (such as halogen (chlorine, bromine or iodine) or OSO₂CF₃).

The compounds of formula (I) may be prepared by reacting a compound offormula (II) with the salt of an oxime of formula (III) under basicconditions. Thus an oxime of general formula (III) may be treated with asuitable base (such as sodium hydride or sodium methoxide), in asuitable solvent (such as N,N-dimethylformamide or tetrahydrofuran), toform the anion and then a compound of formula (II) added.

Oximes of the general formula (III) are known in the chemicalliterature. The compound of general formula (II) where X is bromine andthe propenoate group has the (E)-configuration is described inEP-A-0203606.

Oximes of formula (III) can be prepared by reacting a compound offormula (XI) with hydroxylamine in a suitable solvent (for example amixture of a primary alcohol (such as methanol or ethanol) with water)optionally in the presence of a buffer (such as a salt of an organicacid (for example sodium acetate)).

Compounds of formula (XI) can be prepared by treating a compound offormula (XII) with an acid, preferably a strong mineral acid such ashydrochloric acid of suitable concentration, in a suitable solvent, forexample acetone. Compounds of formula (XII) can be prepared by treatinga compound of formula (XIII) (wherein X is typically chlorine, bromineor OSO₂ CF₃) with an alkoxyvinyl tin (for example(1-ethoxyvinyl)tri-n-butyltin) in the presence of a suitable catalyst(such as bis(triphenylphosphine)palladium(II) chloride) in a suitablesolvent (for example N,N-dimethylformamide).

Alternatively, compounds of formula (XI) can be prepared by reacting acompound of formula (XIV) with a methyl magnesium halide in a suitablesolvent (for example diethyl ether or tetrahydrofuran). Compounds offormula (XIV) can be prepared by reacting a compound of formula (XIII)with a trialkylamine (such as trimethylamine) which is preferably inaqueous solution, and in the presence of a suitable organic solvent (forexample diethyl ether), and then introducing a source of cyanide anions(for example potassium or sodium cyanide).

Alternatively, compounds of formulae (XI), (XII), (XIII) and (XIV) canbe prepared by methods known in the literature.

Alternatively, compounds of formula (I) can be prepared by treating thesubstituted hydroxylamine (XV) (or a salt thereof, for example itshydrochloride salt) with a compound of formula (XI). The substitutedhydroxylamine (XV) wherein A is hydrogen may be prepared as described inEP 0 463 488.

Alternatively compounds of the invention of formula (I) may be preparedby the steps shown in Scheme 2. The terms R¹ and X are as defined above,R⁵ is hydrogen or a metal (such as sodium or potassium), and R is analkyl group. Each transformation is performed at a suitable temperatureand usually, though not always, in a suitable solvent.

The compounds of the invention of formula (I) can be prepared fromphenylacetates of formula (VI) or the ketoesters of formula (X) by thesteps shown in Scheme 2.

Thus compounds of formula (I) can be prepared by treatment ofphenylacetates of formula (VI) with a base (such as sodium hydride orsodium methoxide) and methyl formate. If a species of formula CH₃ L,wherein L is a leaving group such as a halide (chlorine, bromine oriodine), or a CH₃ SO₄ anion, is then added to the reaction mixture,compounds of formula (I) may be obtained. If a protic acid is added tothe reaction mixture, compounds of formula (IX) wherein R⁵ is hydrogen,are obtained. Alternatively the species of formula (IX) wherein R⁵ is ametal (such as sodium), may themselves be isolated from the reactionmixture.

Compounds of formula (IX) wherein R⁵ is a metal can be converted intocompounds of formula (I) by treatment with a species CH₃ L, wherein L isas defined above. Compounds of formula (IX) wherein R⁵ is hydrogen canbe converted into compounds of formula (I) by successive treatment witha base (such as potassium carbonate) and a species of general formulaCH₃ L.

Alternatively, compounds of formula (I) can be prepared from acetals offormula (IV) by elimination of methanol under either acidic or basicconditions. Examples of reagents or reagent mixtures which can be usedfor this transformation are lithium di-isopropylamide; potassiumhydrogen sulphate (see, for example, T. Yamada, H. Hagiwara and H. Uda,J. Chem. Soc. Chemical Communications, 1980, 838, and referencestherein); and triethylamine, often in the presence of a Lewis acid suchas titanium tetrachloride (see, for example, K. Nsunda and L. Heresi, J.Chem. Soc. Chemical Communications, 1985, 1000).

Acetals of formula (IV) can be prepared by treatment of methyl silylketene acetals of formula (V) with trimethyl orthoformate in thepresence of a Lewis acid such as titanium tetrachloride (see, forexample, K. Saigo, M. Osaki and T. Mukaiyama, Chemistry Letters, 1976,769).

Methyl silyl ketene acetals of formula (V) can be prepared fromphenylacetates of formula (VI) by treatment with a base andtrialkylsilyl halide of formula R₃ SiCl or R₃ SiBr, such astrimethylsilyl chloride, or a base (such as triethylamine) and atrialkylsilyl triflate of formula R₃ Si--OSO₂ CF₃ (see, for example, C.Ainsworth, F. Chen and Y. Kuo, J. Organometallic Chemistry, 1972, 46,59).

It is not always necessary to isolate the intermediates (IV) and (V);under appropriate conditions compounds of formula (I) may be preparedfrom phenylacetates of formula (VI) in "one pot" by the successiveaddition of suitable reagents listed above.

Phenylacetates of formula (VI) may be prepared from phenylacetates offormula (VII). Thus, if an oxime of general formula (III) is treatedwith a suitable base (such as sodium hydride or sodium methoxide) andthe phenyl acetates of formula (VII) are added, phenylacetates offormula (VI) are obtained.

Phenylacetates of formula (VII) can be obtained from isochromanones offormula (VIII) by treatment with HX, wherein X is a halogen (such asbromine), in methanol. This transformation may also be accomplished in 2steps if the isochromanone (VIII) is treated with HX in a non-alcoholicsolvent, and the resulting phenylacetic acid is then esterified usingstandard procedures (see, for example, I. Matsumoto and J. Yoshizawa,Jpn. Kokai (Tokkyo Koho) 79 138 536, 27.10.1979, Chem. Abs., 1980, 92,180829h; and G. M. F. Lim, Y. G. Perron and R. D. Droghini, Res. Discl.,1979, 188, 672, Chem. Abs., 1980, 92, 128526t). Isochromanones offormula (VIII) are well known in the chemical literature.

Alternatively, compounds of formula (I) can be prepared by treatment ofketoesters of formula (X) with methoxymethylenation reagents such asmethoxymethylenetriphenylphosphorane (see, for example, W. Steglich, G.Schramm, T. Anke and F. Oberwinkler, EP 0044 448, 4.7.1980).

Ketoesters of formula (X) may be prepared from ketoesters of formula(VI), by treatment with the anion of oximes of general formula (III) asdescribed above. Ketoesters of formula (XVI) are described in EP 0331061.

Therefore, to summarise, Schemes 1 and 2 illustrate certain methods bywhich the oxime ether and the 3-methoxypropenoate moieties,respectively, may be constructed in the final stages of the synthesis ofthe compounds of the invention of formula (I). An alternative finalstage or stages in the synthesis of the compounds of the invention offormula (I) is a modification to the group R¹. Thus, for example, if asubstituent on the group R¹ is a suitably positioned amino group, it maybe converted in the final stages of the reaction sequence throughdiazotisation into a halogen atom.

In a further aspect the present invention provides a process for thepreparation of a compound of formula (I).

In other aspects the present invention provides the intermediatecompounds 2-acetyl-4-(2,2,2-trifluoroethoxy)pyrimidine.

The compounds of the invention are active fungicides and may be used tocontrol one or more of the following pathogens: Pyricularia oryzae onrice. Puccinia recondita, Puccinia striiformis and other rusts on wheat,Puccinia hordei, Puccinia striiformis and other rusts on barley, andrusts on other hosts e.g. coffee, pears, apples, peanuts, vegetables andornamental plants. Erysiphe graminis (powdery mildew) on barley andwheat and other powdery mildews on various hosts such as Sphaerothecamacularis on hops, Sphaerotheca fuliginea on cucurbits (e.g. cucumber),Podosphaera leucotricha on apple and Uncinula necator on vines.Helminthosporium spp., Rhynchosporium spp., Septoria spp., Pyrenophoraspp., Pseudocercosporella herpotrichoides and Gaeumannomyces graminis oncereals. Cercospora arachidicola and Cercosporidium personata on peanutsand other Cercospora species on other hosts, for example, sugar beet,bananas, soya beans and rice. Botrytis cinerea (grey mould) on tomatoes,strawberries, vegetables, vines and other hosts. Alternaria spp. onvegetables (e.g. cucumber), oil-seed rape, apples, tomatoes and otherhosts. Venturia inaequalis (scab) on apples. Plasmopara viticola onvines. Other downy mildews such as Bremia lactucae on lettuce,Peronospora spp. on soybeans, tobacco, onions and other hosts,Pseudoperonospora humuli on hops and Pseudoperonospora cubensis oncucurbits. Phytophthora infestans on potatoes and tomatoes and otherPhytophthora spp. on vegetables, strawberries, avocado, pepper,ornamentals, tobacco, cocoa and other hosts. Thanatephorus cucumeris onrice and other Rhizoctonia species on various hosts such as wheat andbarley, vegetables, cotton and turf.

Some of the compounds show a broad range of activities against fungi invitro. They may also have activity against various post-harvest diseasesof fruit (e.g. Penicillium digitatum and italicum and Trichoderma virideon oranges, Gloeosporium musarum on bananas and Botrytis cinerea ongrapes).

Further, some of the compounds may be active as seed dressings againstFusarium spp., Septoria spp., Tilletia spp., (bunt, a seed-borne diseaseof wheat), Ustilago spp. and Helminthosporium spp. on cereals,Rhizoctonia solani on cotton and Pyricularia oryzae on rice.

The compounds may have systemic movement in plants. Moreover, thecompounds may be volatile enough to be active in the vapour phaseagainst fungi on the plant.

The invention therefore provides a method of combating fungi whichcomprises applying to a plant, to a seed of a plant or to the locus ofthe plant or seed a fungicidally effective amount of a compound ashereinbefore defined, or a composition containing the same.

The compounds may be used directly for agricultural purposes but aremore conveniently formulated into compositions using a carrier ordiluent. The invention thus provides a fungicidal compositioncomprising, as an active ingredient, a compound as hereinbefore definedand a fungicidally acceptable carrier or diluent therefor.

The compounds can be applied in a number of ways. For example, they canbe applied, formulated or unformulated, directly to the foliage of aplant, to seeds or to other medium in which plants are growing or are tobe planted, or they can be sprayed on, dusted on or applied as a creamor paste formulation, or they can be applied as a vapour or as slowrelease granules.

Application can be to any part of the plant including the foliage,stems, branches or roots, or to soil surrounding the roots, or to theseed before it is planted, or to the soil generally, to paddy water orto hydroponic culture systems. The invention compounds may also beinjected into plants or sprayed onto vegetation using electrodynamicspraying techniques or other low volume methods.

The term "plant" as used herein includes seedlings, bushes and trees.Furthermore, the fungicidal method of the invention includespreventative, protectant, prophylactic and eradicant treatments.

The compounds are preferably used for agricultural and horticulturalpurposes in the form of a composition. The type of composition used inany instance will depend upon the particular purpose envisaged.

The compositions may be in the form of dustable powders or granulescomprising the active ingredient (invention compound) and a soliddiluent or carrier, for example, fillers such as kaolin, bentonite,kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia,fuller's earth, gypsum, diatomaceous earth and china clay. Such granulescan be preformed granules suitable for application to the soil withoutfurther treatment. These granules can be made either by impregnatingpellets of filler with the active ingredient or by pelleting a mixtureof the active ingredient and powdered filler.

Compositions for dressing seed may include an agent (for example, amineral oil) for assisting the adhesion of the composition to the seed;alternatively the active ingredient can be formulated for seed dressingpurposes using an organic solvent (for example, N-methylpyrrolidone,propylene glycol or dimethylformamide). The compositions may also be inthe form of wettable powders or water dispersible granules comprisingwetting or dispersing agents to facilitate the dispersion in liquids.The powders and granules may also contain fillers and suspending agents.

Emulsifiable concentrates or emulsions may be prepared by dissolving theactive ingredient in an organic solvent optionally containing a wettingor emulsifying agent and then adding the mixture to water which may alsocontain a wetting or emulsifying agent. Suitable organic solvents arearomatic solvents such as alkylbenzenes and alkylnaphthalenes, ketonessuch as isophorone, cyclohexanone, and methylcyclohexanone, chlorinatedhydrocarbons such as chlorobenzene and trichlorethane, and alcohols suchas benzyl alcohol, furfuryl alcohol, butanol and glycol ethers.

Suspension concentrates of largely insoluble solids may be prepared byball or bead milling with a dispersing agent with a suspending agentincluded to stop the solid settling.

Compositions to be used as sprays may be in the form of aerosols whereinthe formulation is held in a container under pressure of a propellant,e.g. fluorotrichloromethane or dichlorodifluoromethane.

The invention compounds can be mixed in the dry state with a pyrotechnicmixture to form a composition suitable for generating in enclosed spacesa smoke containing the compounds.

Alternatively, the compounds may be used in micro-encapsulated form.They may also be formulated in biodegradable polymeric formulations toobtain a slow, controlled release of the active substance.

By including suitable additives, for example additives for improving thedistribution, adhesive power and resistance to rain on treated surfaces,the different compositions can be better adapted for various utilities.

The invention compounds can be used as mixtures with fertilisers (e.g.nitrogen-, potassium- or phosphorus-containing fertilisers).Compositions comprising only granules of fertiliser incorporating, forexample coated with, the compound are preferred. Such granules suitablycontain up to 25% by weight of the compound. The invention thereforealso provides a fertiliser composition comprising a fertiliser and thecompound of general formula (I) or a salt or metal complex thereof.

Wettable powders, emulsifiable concentrates and suspension concentrateswill normally contain surfactants, e.g. a wetting agent, dispersingagent, emulsifying agent or suspending agent. These agents can becationic, anionic or non-ionic agents.

Suitable cationic agents are quaternary ammonium compounds, for example,cetyltrimethylammonium bromide. Suitable anionic agents are soaps, saltsof aliphatic monoesters of sulphuric acid (for example, sodium laurylsulphate), and salts of sulphonated aromatic compounds (for example,sodium dodecylbenzenesulphonate, sodium, calcium or ammoniumlignosulphonate, butylnaphthalene sulphonate, and a mixture of sodiumdiisopropyl- and triisopropylnaphthalene sulphonates).

Suitable non-ionic agents are the condensation products of ethyleneoxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkylphenols such as octyl- or nonylphenol and octylcresol. Other non-ionicagents are the partial esters derived from long chain fatty acids andhexitol anhydrides, the condensation products of the said partial esterswith ethylene oxide, and the lecithins. Suitable suspending agents arehydrophilic colloids (for example, polyvinylpyrrolidone and sodiumcarboxymethylcellulose), and swelling clays such as bentonite orattapulgite.

Compositions for use as aqueous dispersions or emulsions are generallysupplied in the form of a concentrate containing a high proportion ofthe active ingredient, the concentrate being diluted with water beforeuse. These concentrates should preferably be able to withstand storagefor prolonged periods and after such storage be capable of dilution withwater in order to form aqueous preparations which remain homogeneous fora sufficient time to enable them to be applied by conventional sprayequipment. The concentrates may conveniently contain up to 95%, suitably10-85%, for example 25-60%, by weight of the active ingredient. Afterdilution to form aqueous preparations, such preparations may containvarying amounts of the active ingredient depending upon the intendedpurpose, but an aqueous preparation containing 0.0005% or 0.01% to 10%by weight of active ingredient may be used.

The compositions of this invention may contain other compounds havingbiological activity, e.g. compounds having similar or complementaryfungicidal activity or which possess plant growth regulating, herbicidalor insecticidal activity.

A fungicidal compound which may be present in the composition of theinvention may be one which is capable of combating ear diseases ofcereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporiumspp., seed and soil-borne diseases and downy and powdery mildews ongrapes and powdery mildew and scab on apple, etc. By including anotherfungicide, the composition can have a broader spectrum of activity thanthe compound of general formula (I) alone. Further the other fungicidecan have a synergistic effect on the fungicidal activity of the compoundof general formula (I). Examples of fungicidal compounds which may beincluded in the composition of the invention are(±)-2-(2,4-dichlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propyl1,1,2,2-tetrafluoroethyl ether, (RS)-1-aminopropylphosphonic acid,(RS)-4-(4-chlorophenyl)-2-phenyl-2-(1H-1,2,4-triazol-1-ylmethyl)butyronitrile,(RS)-chloro-N-(cyano(ethoxy)methyl)benzamide,(Z)-N-but-2-enyloxymethyl-2-chloro-2',6'-diethylacetanilide,1-(2-cyano-2-methoxyiminoacetyl)-3-ethyl urea,1-[2RS,4RS;2RS,4RS)-4-bromo-2-(2,4-dichlorophenyl)tetrahydrofurfuryl]-1H-1,2,4-triazole,3-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)quinazolin-4(3H)-one,3-chloro-4-[4-methyl-2-(1H-1,2,4-triazol-1-methyl)-1,3-dioxolan-2-yl]phenyl-4-chlorophenylether,4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide,4-chlorobenzylN-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)thioacetamidate,5-ethyl-5,8-dihydro-8-oxo(1,3)-dioxolo(4,5-g)quinoline-7-carboxylicacid, α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone,anilazine, BAS 454, benalaxyl, benomyl, biloxazol, binapacryl,bitertanol, blasticidin S, bupirimate, buthiobate, captafol, captan,carbendazim, carboxin, chlorbenzthiazone, chloroneb, chlorothalonil,chlorozolinate, copper containing compounds such as copper oxychloride,copper sulphate and Bordeaux mixture, cycloheximide, cymoxanil,cyproconazole, cyprofuram, di-2-pyridyl disulphide 1,1' -dioxide,dichlofluanid, dichlone, diclobutrazol, diclomezine, dicloran,dimethamorph, dimethirimol, diniconazole, dinocap, ditalimfos,dithianon, dodemorph, dodine, edifenphos, etaconazole, ethirimol, ethyl(Z)-N-benzyl-N-([methy(methylthioethylideneaminooxycarbonyl)amino]thio)-.beta.-alaninate,etridazole, fenapanil, fenarimol, fenfuram, fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, flutolanil, flutriafol,fluzilazole, folpet, fosetyl-aluminium, fuberidazole, furalaxyl,furconazole-cis, guazatine, hexaconazole, hydroxyisoxazole, imazalil,iprobenfos, iprodione, isoprothiolane, kasugamycin, mancozeb, maneb,mepronil, metalaxyl, methfuroxam, metsulfovax, myclobutanil, neoasozin,nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol, ofurace,organomercury compounds, oxadixyl, oxycarboxin, penconazole, pencycuron,pent-4-enyl N-furfuryl-N-imidazol-1-ylcarbonyl-DL-homoalaninate,phenazin oxide, phthalide, polyoxin D, polyram, probenazole, prochloraz,procymidone, propamocarb, propiconazole, propineb, prothiocarb,pyrazophos, pyrifenox, pyroquilon, pyroxyfur, pyrrolnitrin,quinomethionate, quintozene, streptomycin, sulphur, techlofthalam,tecnazene, tebuconazole, thiabendazole, thiophanate-methyl, thiram,tolclofos-methyl, triacetate salt of1,1'-iminodi(octamethylene)diguanidine, triadimefon, triadimenol,triazbutyl, tricyclazole, tridemorph, triforine, validamycin A,vinclozolin and zineb. The compounds of general formula (I) can be mixedwith soil, peat or other rooting media for the protection of plantsagainst seed-borne, soil-borne or foliar fungal diseases.

Suitable insecticides which may be incorporated in the composition ofthe invention include buprofezin, carbaryl, carbofuran, carbosulfan,chlorpyrifos, cycloprothrin, demeton-s-methyl, diazinon, dimethoate,ethofenprox, fenitrothion, fenobucarb, fenthion, formothion, isoprocarb,isoxathion, monocrotophos, phenthoate, pirimicarb, propaphos and XMC.

Plant growth regulating compounds are compounds which control weeds orseedhead, formation, or selectively control the growth of less desirableplants (e.g. grasses). Examples of suitable plant growth regulatingcompounds for use with the invention compounds are 3,6-dichloropicolinicacid,1-(4-chlorophenyl-4,6-dimethyl-2-oxo-1,2-dihydropyridine-3-carboxylicacid, methyl-3,6-dichloroanisate, abscisic acid, asulam,benzoylprop-ethyl, carbetamide, daminozide, difenzoquat, dikegulac,ethephon, fenpentezol, fluoridamid, glyphosate, glyphosine,hydroxybenzonitriles (e.g. bromoxynil), inabenfide, isopyrimol, longchain fatty alcohols and acids, maleic hydrazide, mefluidide,morphactins (e.g. chlorfluoroecol), paclobutrazol, phenoxyacetic acids(e.g. 2,4-D or MCPA), substituted benzoic acid (e.g. triiodobenzoicacid), substituted quaternary ammonium and phosphonium compounds (e.g.chloromequat, chlorphonium or mepiquatchloride), tecnazene, the auxins(e.g. indoleacetic acid, indolebutyric acid, naphthylacetic acid ornaphthoxyacetic acid), the cytokinins (e.g. benzimidazole,benzyladenine, benzylaminopurine, diphenylurea or kinetin), thegibberellins (e.g. GA₃, GA₄ or GA₇) and triapenthenol.

The following Examples illustrate the invention. Throughout theExamples, the term `ether` refers to diethyl ether, magnesium sulphatewas used to dry solutions, and solutions were concentrated under reducedpressure. Reactions involving air or water sensitive intermediates wereperformed under an atmosphere of nitrogen and solvents were dried beforeuse, where appropriate. Unless otherwise stated, chromatography wasperformed on a column of silica gel as the stationary phase. Whereshown, infrared and NMR data are selective; no attempt is made to listevery absorption in all cases. ¹ H NMR spectra were recorded using CDCl₃-solutions unless otherwise stated. The following abbreviations are usedthroughout:

    ______________________________________                                        DMF =  .sub.--N, .sub.--N-di-                                                             m.p. = melting point                                                                          t = triplet                                       methylformamide                                                                           ppm = parts per million                                                                       q = quartet                                       NMR = nuclear                                                                             s = singlet     m = multiplet                                     magnetic resonance                                                                        d = doublet     br = broad                                        IR = infrared                                                                 b.p. = boiling point                                                          ______________________________________                                    

EXAMPLE 1

This Example illustrates the preparation of (E),(E)-methyl2-[2-(4-trifluoromethylpyrid-2-yl-acetoximinomethyl)phenyl]-3-methoxypropenoate(Compound No. 4 of Table I).

A solution of 2-chloro-4-trifluoromethylpyridine (3.33 g),(1-ethoxyvinyl)tri-n-butyltin (5.95 g) andbis(triphenylphosphine)palladium(II) chloride (0.4 g) in DMF (40 ml) washeated at 70° C. for 16 hours. The reaction mixture was cooled to roomtemperature, potassium fluoride (60 ml of a 10% aqueous solution) wasadded and the resulting mixture was stirred for 1 hour then filteredthrough Hyflo supercel filter aid which was rinsed through with ether.The filtrate was extracted with ether (×2) and the combined extractswere washed with brine, then dried, concentrated and chromatographedusing ether:hexane 1:4 as the eluant to give1-ethoxy-1-(4-trifluoromethylpyrid-2-yl)-ethylene (1.4 g, 35% yield) asa pale yellow liquid; ¹ H NMR (270 MHz): δ1.45(3H,t), 4.00(2H,q),4.42(1H,d), 5.50(1H,d), 7.40(1H,d), 7.88(1H,s), 8.72(1H,d) ppm.

A solution of 1-ethoxy-1-(4-trifluoromethylpyrid-2-yl)-ethylene (1.4 g)in acetone (15 ml) was treated with hydrochloric acid (5 ml of a 2Msolution). The reaction mixture was allowed to stand for 16 hours thenconcentrated, diluted with water and neutralised with sodiumbicarbonate. The aqueous phase was extracted with ether (×2) and thecombined extracts were washed with brine, dried and concentrated to give2-acetyl-4-trifluoromethylpyridine (1.2 g, 99% yield) as a pale yellowliquid. IR maximum (film): 1705 cm⁻¹.

A solution of 2-acetyl-4-trifluoromethylpyridine (1.2 g), hydroxylamine(0.495 g) and sodium acetate (2.2 g) in a mixture of ethanol:water(20:10 ml) was heated under reflux for 2 hours. The reaction mixture waspoured into water and extracted with ethyl acetate (×2). The combinedextracts were washed with water, dried and concentrated to give a solidwhich was washed with hexane to give(E)-2-acetyl-4-trifluoromethylpyridine oxime (1.0 g, 77% yield) as apale pink solid; ¹ H NMR (270 MHz): δ2.39(3H,s), 7.47(1H,d),7.89(1H,brs), 8.12(1H,s), 8.12(1H,s), 8.78(1H,d); ppm.

A solution of 2-acetyl-4-trifluoromethylpyridine oxime (0.66 g) in DMF(10 ml) was added dropwise to a stirred suspension of sodium hydride(0.078 g) in DMF (20 ml). An hour later, the reaction mixture was cooledto 0° C. and a solution of(E)-methyl-2-[2-(bromomethyl)phenyl]-3-methoxypropenoate (0.92 g) in DMF(10 ml) was added dropwise. After a further 2 hours, the reactionmixture was poured into water and extracted with ether (×3). The organicextracts were washed with brine, dried, concentrated and chromatographedusing ethyl acetate:hexane 3:7 as the eluant to give the title compound(0.844 g, 64% yield) as a colourless oil; IR maxima (film): 1708, 1633cm⁻¹ ; ¹ H NMR (270 MHz): δ2.33(3H,s), 3.69(3H,s), 3.82(3H,s),5.20(2H,s), 7.18(1H,m), 7.35(2H,m), 7.45(1H,d), 7.50(1H,m), 7.61(1H,s),8.14(1H,s), 8.75(1H,d) ppm.

EXAMPLE 2

This Example illustrates the preparation of (E),(E)-methyl2-[2-(4-ethoxypyrimidin-2-yl-acetoximino-methyl)phenyl]-3-methoxypropenoate(Compound No. 6 of Table I).

A solution of 2-chloro-4-ethoxypyrimidine (6.34 g),(1-ethoxyvinyl)-tri-n-butyltin (14.4 g) andbis(triphenylphosphine)palladium(II) chloride (1 g) in DMF (60 ml) washeated at 90° C. for 60 hours. The reaction mixture was cooled to roomtemperature and potassium fluoride (100 ml of a 10% aqueous solution)was added. The resulting mixture was stirred for 1 hour then filteredthrough Hyflo supercel filter aid which was rinsed through with ether.The filtrate was extracted with ether (×2) and the combined extractswere washed with brine, then dried, concentrated and chromatographedusing ethyl acetate:hexane 1:4 as the eluant to give1-ethoxy-1-(4-ethoxypyrimidin-2-yl)-ethylene (2.7 g, 35% yield) as anorange oil; IR maximum (film): 1550cm⁻¹ ; ¹ H NMR (270 MHz):δ1.40(3H,t), 1.50(3H,t), 4.02(2H,q), 4.45(2H,q), 4.58(1H,d), 5.65(1H,d),6.60(1 H,d), 8.48(1H,d) ppm.

A solution of 1-ethoxy-1-(4-ethoxypyrimidin-2-yl)-ethylene (2.7 g) inacetone (20 ml) was treated with hydrochloric acid (6 ml of a 2Msolution). The reaction mixture was allowed to stand for 16 hours, thenwarmed at 40° C. for 11/2 hours, and concentrated. The residue wasdiluted with water and neutralised with sodium bicarbonate. The aqueousphase was extracted with ethyl acetate (×2) and the combined extractswere washed with brine, dried and concentrated to give2-acetyl-4-ethoxypyrimidine (1.8 g, 78% yield) as a colourless oil whichpartially solidified on standing, and was used without furtherpurification; IR maximum (film): 1717cm⁻¹ ; ¹ H NMR (270 MHz):δ1.45(3H,t), 2.74(3H,s), 4.53(2H,q), 6.85(1H,d), 8.60(1H,d) ppm.

A solution of 2-acetyl-4-ethoxypyrimidine (1.8 g), hydroxylaminehydrochloride (0.83 g) and sodium acetate (2.2 g) in a mixture ofethanol:water (30:10 ml) was heated under reflux for 3 hours. Thereaction mixture was then poured into water and extracted with ethylacetate (×3). the combined extracts were washed with brine, dried andconcentrated to give a solid which was washed with hexane to give(E)-2-acetyl-4-ethoxypyrimidine oxime as an off-white solid (1.15 g, 60%yield); ¹ H NMR (270 MHz): δ1.44(3H,t), 2.38(3H,s), 4.50(2H,q),6.68(1H,d), 8.48(1H,d), 9.80(1H,brs) ppm.

A solution of 2-acetyl-4-ethoxy-pyrimidine oxime (0.8 g) in DMF (15 ml)was added dropwise to a stirred suspension of sodium hydride (0.10 g) inDMF (10 ml). An hour later, the reaction mixture was cooled to 0° C. anda solution of (E)-methyl 2-[2-(bromomethyl)phenyl]-3-methoxypropenoate(1.22 g) in DMF (15 ml) was added dropwise. After a further 2 hours themixture was poured into water and extracted with ether (×3). The organicextracts were washed with brine, dried, concentrated and chromatographedusing ethyl acetate:hexane 3:2 as the eluant to give the title compound(0.84 g, 51% yield) as a white solid, m.p. 87°-89° C.; IR maxima (nujolmull): 1698, 1623 cm¹ ; ¹ H NMR (270 MHz): δ1.42(3H, t), 2.33(3H,s),3.68(3H,s), 3.82(3H,s), 4.46(2H,q), 5.30(2H,s), 6.65 (1H,d), 7.18(1H,m),7.34(2H,m), 7.55(1H,d), 7.58(1H,s), 8.50(1H,d) ppm.

The 2-acetyl-4-ethoxypyrimidine used in this example has also beenprepared as follows.

A solution of 2-chloro-4-ethoxy pyrimidine (20 g from the reaction of 1equivalent of sodium ethoxide with 2,4-dichloropyrimidine at 0°-5° C.)in ether (50 ml) was added to ice cooled trimethylamine (50 ml of a 30%aqueous solution). After stirring the mixture for 2 hours a solution ofpotassium cyanide (9.0 g) in water (50 ml) was added and the resultingmixture was stirred vigorously at room temperature. After 16 hours thereaction mixture was extracted with ether (3×50 ml) and the combinedextracts were washed with brine, dried and concentrated to give2-cyano-4-ethoxypyrimidine (14.6 g, 77% yield) as a pale yellow liquidwhich gradually crystallised (m.p. 35° C.); ¹ H NMR (270 MHz):δ1.42(3H,t), 4.49(2H,q), 6.89(1H,d), 8.49(1H,d) ppm.

Methyl magnesium bromide (4.4 ml of a 3M solution in ether) was added toa solution of 2-cyano-4-ethoxypyrimidine in THF (20 ml) at -50° C. After1 hour the reaction mixture was quenched by adding hydrochloric acid (10ml of a 2M solution) followed by sodium bicarbonate to produce a neutralsolution. This mixture was extracted with ether (×3) and the combinedextracts were washed with water, dried and concentrated to give a darkgum, bulb to bulb distillation of this gum gave2-acetyl-4-ethoxypyrimidine (1.35 g, 64% yield) as a white low meltingsolid (b.p. 70°-80° C. at 0.1 mmHg).

EXAMPLE 3

This Example illustrates the preparation of (E),(E)-methyl2-[2-(4-[2,2,2-trifluoroethoxy]-pyrimidin-2-yl-acetoximino-methyl)phenyl]-3-methoxypropenoate(Compound No 25 of Table I).

2,2,2-Trifluoroethanol (51.3 ml) in DMF (135 ml) was added to asuspension of sodium hydride (29.5 g) in DMF (335 ml) keeping thetemperature below 10° C. After 1 hour the resulting mixture was added toa solution of 2,4-dichloropyrimidine (100 g) in DMF (330 ml) keeping thetemperature between -5° and -10° C. 1 Hour later the resulting reactionmixture was poured into water (1 l) and extracted with ethyl acetate(3×400 ml). The combined extracts were washed with brine, dried andconcentrated to give 70% pure2-chloro-4-(2,2,2-trifluoroethoxy)-pyrimidine (142 g) as a pale orangeoil; ¹ H NMR (270 MHz): δ4.78(2H,q), 6.83(1H,d), 8.42(1H,d) ppm.

The 2-chloro-4-(2,2,2-trifluoroethoxy)-pyrimidine (142 g) in toluene(330 ml) was added to trimethylamine (140 ml of a 45% aqueous solution)at 0° C. After stirring for 16 hours the organic phase was separatedoff. The aqueous phase was added to toluene (330 ml) then a solutionpotassium cyanide (44 g in 170 ml water) was added at 0° C. The reactionmixture was stirred for a further 16 hours and then the organic phasewas separated, the aqueous was extracted with ether (2×200 ml) and thecombined organic extracts were dried and concentrated to give2-cyano-4-(2,2,2-trifluoroethoxy)-pyrimidine (73.5 g, 77% yield) as ayellow oil; ¹ H NMR (270 MHz): δ4.85(2H,q), 7.10(1H,d), 8.64(1H,d) ppm.

Methyl magnesium bromide (115 ml of a 3.0M solution in ether) was addedto 2-cyano-4-(2,2,2-trifluoroethoxy)-pyrimidine (70.0 g) in THF (300 ml)at -40° C. After the addition it was stirred for 11/2 hours at -40° C.then treated with water (50 ml), followed by enough 2M hydrochloric acidto make the reaction mixture just acid, this was stirred for 11/2 hoursand then neutralised with sodium bicarbonate, and extracted with ether(3×300 ml). The combined ether extracts were dried and concentrated togive 2-acetyl-4-(2,2,2-trifluoroethoxy)-pyrimidine (66.8 g, 88% yield)as a brown oil; IR maxima (film): 1718 cm⁻¹ ; ¹ H NMR (270 MHz):δ2.74(3H,s), 4.92(2H,q), 7.05(1H,d), 8.74(1H,d) ppm.

2-Acetyl-4-(2,2,2-trifluoroethoxy)-pyrimidine (0.47 g) was dissolved ina mixture of ethanol (10 ml) and water (5 ml) and heated to 40° C. for 1hour with hydroxylamine hydrochloride (0.16 g) and sodium acetate (0.43g). The reaction mixture was poured into water and extracted with ethylacetate (3×50 ml). The combined extracts were dried and concentrated.The residue was washed with hexane to give2-acetyl-4-(2,2,2-trifluoroethoxy)-pyrimidine oxime (0.35 g, 70% yield)as a white solid, m.p. 179°-181° C.; ¹ H NMR (270 MHz): δ2.39(3H,s),4.87(2H,q), 6.88(1H,d), 8.60(1H,d) ppm.

A solution of 2-acetyl-4-(2,2,2-trifluoroethoxy)-pyrimidine oxime (0.347g) in DMF (5 ml) was added dropwise to a stirred suspension of sodiumhydride (0.035 g) in DMF (5 ml). 11/2 Hours later, the reaction mixturewas cooled to 0° C. and a solution of (E)-methyl2-[2-(bromomethyl)phenyl]-3-methoxypropenoate (0.4 g) in DMF (5 ml) wasadded dropwise. After 24 hours the mixture was poured in water andextracted with ethyl acetate (×3). The organic extracts were washed withbrine, dried, concentrated and chromatographed using ethylacetate:hexane 4:1 as the eluant to give the title compound (0.3 g, 49%yield) as a white solid, m.p. 90°-92° C.; IR maxima (nujol mull): 1696,1636 cm⁻¹ ; ¹ H NMR (270 MHz): δ2.35(3H,s), 3.68(3H,s), 3.82(3H,s),4.85(2H,q), 5.31(2H,s), 6.82(1H,d), 7.18(1H,m), 7.34(2H,m), 7.55(1H,m),7.59(1H,s), 8.64(1H,d) ppm.

EXAMPLE 4

The compounds were tested against a variety of foliar fungal diseases ofplants. The technique employed was as follows.

The plants were grown in John Innes Potting Compost (No. 1 or 2) in 4 cmdiameter minipots. The test compounds were formulated either by beadmilling with aqueous Dispersol T or as a solution in acetone oracetone/ethanol which was diluted to the required concentrationimmediately before use. For the foliage diseases, the formulations (100ppm active ingredient) were sprayed onto the foliage and applied to theroots of the plants in the soil. The sprays were applied to maximumretention and the root drenches to a final concentration equivalent toapproximately 40 ppm a.i. in dry soil. Tween 20, to give a finalconcentration of 0.05%, was added when the sprays were applied tocereals.

For most of the tests the compound was applied to the soil (roots) andto the foliage (by spraying) one or two days before the plant wasinoculated with the disease. Exception to this were the test on Erysiphegraminis in which the plants were inoculated 24 hours before treatment,and in the test against Puccinia recondita for compounds Nos. 13 and23-54, the plants were inoculated with the disease 48 hours beforetreatment. Foliar pathogens were applied by spray as spore suspensionsonto the leaves of test plants. After inoculation, the plants were putinto an appropriate environment to allow infection to proceed and thenincubated until the disease was ready for assessment. The period betweeninoculation and assessment varied from four to fourteen days accordingto the disease and environment.

The disease control was recorded by the following grading:

4=no disease

3=trace-5% of disease on untreated plants

2=6-25% of disease on untreated plants

1=26-59% of disease on untreated plants

0=60-100% of disease on untreated plants

The results are shown in Table III.

                  TABLE III                                                       ______________________________________                                        Com-                                                                          pound Table                                                                   No    No      Pr    Egh  Egt  Sn  Po  Tc  Vi  Ca  Pv  Pil                     ______________________________________                                              I       4     4             4       4       4   3                        2    I       4          4    3   3       4       4   1                        3    I       4          4    4   4       4       4   4                        4    I       4          4    4   4       4       4   0                        5    I       4          4    4   4   4   4       4   3                        6    I       4          4    0   4       4       4   4                        7    I       4.sup.a    4.sup.a                                                                            0.sup.a                                                                           4.sup.a                                                                           3.sup.a                                                                           4.sup.a 4.sup.a                                                                           2.sup.a                  8    I       4          4    4   4   4   4       4   3                        9    I       4          4    4   4   4   4       4   2                       10    I       4          4    4   4   4   4       4   3                       11    I       2          4    4   3   4   -       4   --                      12    I       4.sup.a    4.sup.a                                                                            4.sup.a                                                                           4.sup.a                                                                           1.sup.a                                                                           4.sup.a 4.sup.a                                                                           0.sup.a                 13    I       4          4    4   4   4   4       4   2                       14    I                  4    3   4   4   4       4   4                       15    I       4          4    4   4   4           4                           16    I                  4    4   4   4   4       4   4                       17    I                  4    4   4   4   4       4   3                       18    I       4          4    4   4   4   4       4   1                       19    I       2          4    4   2   4           4   0                       20    I       4          4    3   4   4   4       4   0                       21    I       0          0    4   4   4   4       4   4                       22    I       4          4    4   4   2   4       4   1                       23    I       4          4    4   4   4   4       4   4                       24    I       4          4    4   4   4   4       4   4                       25    I       4          4    4   4   4   4       4   4                       26    I       4               4   4       4       4   4                       27    I       4          4    4   4   4   4       4                           28    I       4          4    4   4   4   4       4                           29    I       4          4    4   4   4   4       4   4                       30    I       4          4    4   4   4   4       4   4                       31    I       4          4    4   4   4   4       4   4                       32    I       4          4    4   4       4       4   0                       33    I       4          4    4   2       4       4   4                       34    I       4          4    4   3       4       4   4                       35    I       4          4    4   4   4   4       4   4                       36    I       2          3    1   2   3   4       --  0                       37    I       4          4    4   4   4   4       --  4                       38    I       4          4    4   4   4   4       --  4                       39    I       4          4    4   4   4   4       --  1                       40    I       4          4    4   4   4   4       --  4                       41    I       4          4    4   4   4   0       --  0                       42    I       4          4    4   4   4   4       4   4                       43    I       4          4    4   --  4   4       4   1                       44    I       4          4    4   4   4   4       4   4                       45    I       4          4    4   0   4   4       4   4                       46    I       4          4    4   4   4   4       4   4                       47    I       1          4    4   1   4   --      4   --                      48    I       4          4    4   4   4   4       4   4                       50    I       4          4    4   4   4   4       4   4                       ______________________________________                                         a = 10 ppm foliar spray only                                                  Key to Diseases                                                               Pr Puccinis recondita                                                         Tc Thanetophorus cucumeris                                                    Egh Erysiphe graminis hordei                                                  Vi Venturia inaegualis                                                        Egt Erysiphe graminis tritici                                                 Ca Cercospora arachidicola                                                    Sn Septoria nodorum                                                           Pv Plasmopara viticola                                                        Po Pyricularia oryzae                                                         Pil Phytophthora infestans lycopersici                                        ##STR2##

We claim:
 1. A compound of the formula (I):wherein R¹ is: (i) pyrid-2-ylsubstituted by one or more groups selected from C₁₋₆ alkoxy, C₁₋₆haloalkyl, C₁₋₆ haloalkoxy, C₁₋₄ alkoxy(C₁₋₆)alkyl or C₁₋₄alkoxy(C₁₋₆)alkoxy; ##STR3## wherein Y¹ is C₂₋₆ alkyl, C₁₋₆ haloalkyl,C₁₋₆ alkoxy, C₁₋₆ alkylthio, C₁₋₆ alkylsulphinyl, C₁₋₆ haloalkoxy, C₁₋₆alkoxy(C₁₋₆)alkyl, C₁₋₆ alkoxy(C₁₋₆)alkoxy, C₁₋₄alkoxy(C₁₋₆)alkoxy(C₁₋₆)alkoxy, di(C₁₋₄ alkoxy)(C₁₋₆)alkoxy, C₂₋₆alkenyloxy or C₂₋₆ alkynyloxy and Z¹ is hydrogen, fluorine, chlorine orC₁₋₆ alkyl; or Y¹ is methyl and Z¹ is fluorine, chlorine or C₁₋₆ alkyl;or, ##STR4## wherein Y² is C₂₋₆ alkyl, C₁₋₆ haloalkyl, C₂₋₆ alkoxy, C₁₋₆alkylthio, C₁₋₆ alkylsulphinyl, C₁₋₆ haloalkoxy or C₂₋₄ alkynyloxy andZ² is hydrogen, fluorine, chlorine or C₁₋₄ alkyl; or Y² is methyl ormethoxy and Z² is fluorine, chlorine or C₁₋₄ alkyl.
 2. A compound asclaimed in claim 1 wherein Y¹ is C₂₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆alkoxy, C₁₋₆ alkylthio, C₁₋₆ alkylsulphinyl, C₁₋₆ haloalkoxy or C₂₋₄alkynyloxy and Z¹ is hydrogen, fluorine, chlorine or C₁₋₄ alkyl; or Y¹is methyl and Z¹ is fluorine, chlorine or C₁₋₄ alkyl.
 3. A compound asclaimed in claim 1 wherein Y¹ is C₂₋₆ alkoxy or C₁₋₆ haloalkoxy and Z¹is hydrogen, chlorine, fluorine or methyl.
 4. A compound as claimed inclaim 1 wherein Y² is C₂₋₆ alkoxy or C₁₋₆ haloalkoxy and Z² is hydrogen,chlorine, fluorine or methyl.
 5. A compound as claimed in claim 1wherein R¹ is 6-trifluoromethylpyrid-2-yl (compound No. 2),4-trifluoromethylpyrid-2-yl (compound No. 4),4-trifluoromethylpyrimidin-2-yl (compound No. 5), 4-ethoxypyrimidin-2-yl(compound No. 6), 4-methoxypyrid-2-yl (compound No. 8),4-methylthiopyrimidin-2-yl (compound No. 9), 4-methoxypyrimidin-2-yl(compound No. 10), 4-propargyloxypyrimidin-2-yl (compound No. 11),4-n-propyloxypyrimidin-2-yl (compound No. 12),4-n-butyloxypyrimidin-2-yl (compound No. 13),3-trifluoromethylpyrid-2-yl (compound No. 14),4-iso-propyloxypyrimidin-2-yl (compound No. 15), 4-ethoxypyrid-2-yl(compound No. 16), 4-ethylthiopyrimidin-2-yl (compound No. 17),3-methoxypyrid-2-yl (compound No. 18), 3-ethoxypyrid-2-yl (compound No;19), 6-methoxypyrid-2-yl (compound No. 20), 6-ethylpyrimidin-4-yl(compound No. 21), 4-ethoxy-5-methylpyrimidin-2-yl (compound No. 22),4-iso-propyloxypyrid-2-yl (compound No. 23),6-iso-propyloxypyrimidin-4-yl (compound No. 24),4-(2,2,2-trifluoroethoxy)pyrimidin-2-yl (compound No. 25),4-methoxyethoxypyrid-2-yl (compound No. 27),4-methoxy-5-methylpyrimidin-2-yl (compound No. 28),5-trifluoromethylpyrid-2-yl (compound No. 29),4-iso-propyloxy-5-methyl-pyrimidin-2-yl (compound No. 30),4-(2,2,2-trifluoroethoxy)-5-methylpyrimidin-2-yl (compound No. 31),6-ethoxypyrid-2-yl (compound No. 32), 4-ethoxy-5-fluoropyrimidin-2-yl(compound No. 33), 4-methoxy-5-fluoropyrimidin-2-yl (compound No. 34)6-(2,2,2-trifluoroethoxy)pyrimidin-4-yl (compound No. 35),4-trifluoromethyl-6-(2,2,2-trifluoroethoxy)pyrid-2-yl (compound No. 36),4-(2,2,2-trifluoroethoxy)-5-fluoropyrimidin-2-yl (compound No. 37),4-isopropyloxy-5-fluoropyrimidin-2-yl (compound No. 38),4-trifluoromethyl-6-ethoxypyrid-2-yl (compound No. 39),4-(2,2,3,3-tetrafluoro-n-propyloxy)pyrimdin-2-yl (compound No. 40),4-trifluoromethyl-6-methoxypyrid-2-yl (compound No. 41),4-(2,2,2-trifluoroethoxy)pyrid-2-yl (compound No. 42) or5-iso-propyl-6-methoxypyrimidin-4-yl (compound No. 43).
 6. Theintermediate compound 2-acetyl-4-(2,2,2-trifluoroethoxy)pyrimidine.
 7. Afungicidal composition comprising, as an active ingredient, a compoundas claimed in claim 1 and a fungicidally acceptable carrier of diluenttherefor.
 8. A process for combating fungi which comprises applying to aplant, to a seed of a plant or to the locus thereof, a fungicidallyeffective amount of a compound as claimed in claim 1.